Rosenbaum , N , Schmidt , L , Mohr , F , Fuhr , O , Nieger , M & Bräse , S 2021 , ' Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction ' , European Journal of Organic Chemistry , vol. 2021 , no. 10 , pp. 1568-1574 . https://doi.org/10.1002/ejoc.202100035
Title: | Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction |
Author: | Rosenbaum, Nicolai; Schmidt, Lisa; Mohr, Florian; Fuhr, Olaf; Nieger, Martin; Bräse, Stefan |
Contributor organization: | Department of Chemistry |
Date: | 2021-03-12 |
Language: | eng |
Number of pages: | 7 |
Belongs to series: | European Journal of Organic Chemistry |
ISSN: | 1434-193X |
DOI: | https://doi.org/10.1002/ejoc.202100035 |
URI: | http://hdl.handle.net/10138/328116 |
Abstract: | In this study, we report a convenient and high yielding formal semisynthesis of demethylgorgosterol, a marine steroid with an intriguing sidechain containing a cyclopropane unit. This was achieved through the synthesis of an advanced ketone intermediate. The synthetic route features a total of ten steps, starting from commercially available stigmasterol, with an overall yield of 27 %. The key step was a stereoselective intermolecular cyclopropanation reaction. This reaction proceeded in 82 % yield, the resulting cyclopropane carboxylic ester shows a trans/cis ratio of 89 : 11, with a diastereomeric ratio for the trans-diastereomers of >99 : 1. A reduction/oxidation sequence afforded the corresponding aldehyde, which was used in a Grignard reaction. A final oxidation step then yielded the desired ketone. This novel route presents a platform to further investigate the medicinal applications of gorgosterol-type steroids and to fully understand their role in coral symbiosis. |
Subject: |
Cyclopropanation
Gorgosterol Steroids Stereoselective synthesis Ruthenium 116 Chemical sciences |
Peer reviewed: | Yes |
Rights: | cc_by |
Usage restriction: | openAccess |
Self-archived version: | publishedVersion |
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